US2736749A - Dye-fixing agents - Google Patents
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- US2736749A US2736749A US292741A US29274152A US2736749A US 2736749 A US2736749 A US 2736749A US 292741 A US292741 A US 292741A US 29274152 A US29274152 A US 29274152A US 2736749 A US2736749 A US 2736749A
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/56—Condensation products or precondensation products prepared with aldehydes
Definitions
- the present invention relates to. the preparation of I guanidine-formaldehyde condensation products suitable for use in improving the washfastness of substantive dyestufis on cellulosic materials.
- the principal object of the present invention is the provision of a guanidine-formaldehyde condensation product which is uniquely superior to the guanidine-formaldehyde condensation products and other dye-fixatives hitherto available. 4
- a further object of the invention is the preparation of guanidine-formaldehyde dye-fixing agents which are highly substantive and will enhance the fastness of dyeings sufficiently to withstand themost strenuous of washing conditions.
- Another important object of the present invention is to provide novel procedures for producing such guanidine-formaldehyde condensation products of superior dyefixing characteristics.
- Still another object of the invention is the provision of a guanidine-formaldehyde condensation product which, in addition to providing maximum dye-fixation, otfers the further advantages over prior dye-fixing agents of being readily soluble, neutral in pH, stable to storage and nonsensitive to sulfate ions.
- the foregoing objects are accomplished, in accordance with the present invention, by reacting an aqueous solution of guanidine and formaldehyde under mild conditions of temperature and time.
- the resulting reaction mixture after neutralization with acid and solubilization by heating, may be used in the aftertreatment of previously dyed cellulosic materials-in conventional manner to render substantive dyeings highly washfast.
- the success of the invention resides, at least to a substantial extent, 'in the discovery that mild reaction conditions are essential for producing a condensation product showing maximum washfastness. More partiwlarly, it has been found that if the reaction between guanidine and formaldehyde is etfected at a temperature not greater than 2 about 80' C., rather than at the refluxing temperatures conventionally employed, for a relatively moderate time, dependent upon the temperature employed, condensation products possessing unusually superior dye-fixing properties can be obtained. The duration of the condensation reaction varies inversely over a fairly wide range, according to the particular temperature employed.
- the reaction time should not exceed fifteen minutes in order to obtain a condensation product of optimum dye-fixingcharacteristics. Somewhat inferior products are obtained when the reaction is carried out at this temperature for more than fifteen minutes, e. g., one-half hour, and a poor dye-fixative is obtained if the reaction is carried out at 80' C. for an hour or more.
- temperatures below the upper limit e. g., 20 to 35' C.
- the reaction must, of course, be longer than that at 80 C. to give the best products.
- the reaction times at these lower temperatures should not be less than six hours, and excellent results have been obtained using reaction times of 20 to 24 hours at these temperatures.
- reaction times at the relatively low temperature employed, can be viewed as being mild reaction conditions, while reaction time of an hour or so at 80 C. should be considered vigorous conditions.
- the present invention contemplates reacting guanidine and formaldehyde at a temperature up to about 80 C. for periods of time ranging from up to fifteen minutes at 80 C. to a period of at least six hours, and preferably about twenty to twenty-four hours, at temperatures of about 20 to 35 C.
- Example I This example is illustrative of a preferred procedure of carrying out the present invention.
- reaction mixture was refluxed for ten minutes and cooled. A total of 31 grams (0.52 mole) of glacial acetic acid was used. The clear, colorless solution weighed 637 grams.
- Example II In a manner similar to that described in Example I, grams (0.50 mole) of guanidine carbonate was added to a solution of 44 grams l.l moles) of sodium hydroxide in 300 grams of water. Reaction with 162 grams (2.0 moles) of formaldehyde solution at'50". C. for one hour was followed by neutralization and solubilization as in Example I; grams (1.75 moles) of glacial acetic acid was used. Aftertreatment of dyed cotton fabric with the resulting product afiorded outstanding fastness to washing.
- Example Ill Following a procedure similar to that described in Example I, 122 grams (1.0 mole) of guanidine nitrate was added to a solution of 40 grams (l.0 mole) of sodium hydroxide in Til-grams of water. After reaction with 162 grams (2 moles) of formaldehyde solution at 50 C. for one hour, neutralization and solubilization were carried out as in Example I; 36 grams of glacial acetic acid was required.
- Example I Use of the product obtained above in the after-treatment of a dyed cotton fabric as outlined in Example I rendered the dyeing substantially washfast.
- Example I V Free guanidine was obtained by stirring 360 grams (2 moles) of guanidine carbonate in 1300 ml. of water with 800 grams (2.5 moles) of finely ground barium hydroxide hydrate until complete reaction. The mixture was filtered and the solution balanced by adding sulfuric acid until a filtered sample gave no precipitate with sulfuric acid or barium chloride.
- Example V Forty-eight grams (0.50 mole) of guanidine hydrochloride was added to a solution of 18 grams (0.45 mole) of sodium hydroxide in 448 grams of water in a manner similar to that described in Example I. Reaction with 81 grams (1.0 mole) of formaldehyde solution at 50 C. for three hours was followed by neutralization and solubilization as before. dyed with a substantive dyestuff in the manner described in Example I, except that, in this case, twice the quantity of the solubilized product was employed, resulted in a dyeing which was substantially unaffected by exposure to No. 3 AATCC Wash Test conditions.
- Example VI An identical procedure to that described in Example IV was followed, except that the condensation reaction was carried out at 65 C. for one hour. The resulting product gave results substantially identical with those of the product of Example I.
- Example VII the pH 6 to 6.5 while heating (47 grams was used).
- Example VIII An identical procedure to that described in Example VII was followed, except that neutralization to pH 7 to 7.5 was accomplished with 32 grams of dilute sulfuric acid solution containing 21 grams of concentrated sulfuric acid with substantially equivalent results.
- Example X The procedure of'Example I was followed, except that in place of sodium hydroxide, 62.5 grams of potassium hydroxide (U. S. P. pellets) was used and the amount of water was 267 grams. Results substantially identical to those shown in Example I were obtained.
- Example XI Following a procedure similar to that described in Example I, 95.5 grams (1.0 mole) of guanidine hydrochloride was added to a solution of 40 grams (1.0 mole) of sodium hydroxide in 298 grams of water. After reaction with 162 grams (2.0 moles) of formaldehyde solution at 50 C. for one hour, the reaction mixture was cooled and allowed to stand at to C. for eighteen 'hours. The granular-like insoluble was removed by filtration and dried at room temperature to give a product weighing 87 grams. For use, 1.0 gram of this product was dissolved in 3000 ml. of water heated to 65 C. and,
- Example XII An identical procedure to that described in Example IV was followed, except that the condensation reaction was allowed to take place at 30 to 35 C. for sixteen hours. The resulting product gave results substantially identical with those of the product of Example IV.
- Example XIII Following a procedure similar to that described in Example I, 95.5 grams (1 mole) of guanidine hydrochloride was added to a solution of 38 grams (0.95 mole) of sodium hydroxide in 302 grams of Water. After reaction with 170 grams (2.1 moles) of formaldehyde solution at 50 C. for one hour, 70% hydroxyacetic acid was added to a pH of 6 and then as required to maintain the pH between 6 and 6.5 while heating (56 grams of acid was used). A ten minute reflux period afforded a clear colorless solution which, when used in the manner of Example I, gave a substantially washfast substantive dyeing on cotton fabric.
- Example XIV This example is illustrative of the results obtained using a procedure wherein, in contrast to the present invention, vigorous reaction conditions are employed.
- Example IV A procedure identical with that described in Example IV was followed, except that a reaction temperature of C. was maintained for one hour. Substantive aftertreatme'nt with the product thus obtained resulted in poor washfastness, compared to that obtained using the product of Example IV.
- aqueous solution of guanidine and formaldehyde used in the process of the invention can be prepared in any convenient manner.
- free guanidine may be dissolved in water and the desired proportion of formaldehyde, in aqueous solution, added thereto.
- the reaction mixture is obtained in the preferred manner illustrated in the preceding examples, i. e., by adding aqueous formaldehyde to an aqueous solution of guanidine prepared by reacting a guanidine salt, such as the hydrochloride, nitrate or carbonate, with an approximately equivalent amount of a base stronger than guanidine, e. g., sodium or potassium hydroxide or with a compound, such as barium or calcium hydroxide, which reacts to form an insoluble salt capable of being separated from the guanidine solution.
- a guanidine salt such as the hydrochloride, nitrate or carbonate
- Formaldehyde as such or in the form of its polymers, such as paraformaldehyde, may be used for reaction with the guanidine, in accordance with the present invention.
- the amount of formaldehyde utilized is between 1.5 and 3.5 moles per mole of guanidine, although, preferably, there is employed from 1.8 to 2.5 moles of formaldehyde for each mole of guanidine.
- the resulting condensation product may be solubilized and, thereafter, applied to dyed cellulosic materials in any conventional fashion.
- solubilization is accomplished by adding to the reaction mixture an appropriate acid, such as formic, acetic, lactic, hydrochloric, sulfuric, or hydroxyacetic, the last being preferred, to a pH of about to 9, and preferably to a pH on the acid side of the stated range.
- an appropriate acid such as formic, acetic, lactic, hydrochloric, sulfuric, or hydroxyacetic, the last being preferred, to a pH of about to 9, and preferably to a pH on the acid side of the stated range.
- the reaction mixture is refluxed until the condensation product is dissolved and a clear, colorless solution is obtained.
- This solution may then be used as an aftertreatment for dyed cellulosic fabric at a concentration of about 1% (calculated as organic solids on the weight of cloth) preferably in conjunction with known copper compounds.
- the latter may be recovered in solid form from the reaction mixture by filtration, thereafter dried and then dissolved in hot water for use in aftertreating dyed cellulosic materials in the manner above described. In either case, the washfastness of dyeings treated with the condensation products of the invention is remarkably superior to the washfastness of dyeings treated with the previously available dye-fixatives.
- a process for the production of guanidine-formaldehyde condensation products which comprises heating time ranging from up to fifteen minutes at 80 C. to
- reaction time varying inversely with the reaction temperature and having a maximum of about 24 hours at 20 C., thereafter neutralizing said reaction mixture by addition of acid thereto to a pH of between 5 and 9 and heating said reaction mixture until a clear solution is obtained.
- a process for the production of guanidine-formaldehyde condensation products which comprises heating an aqueous reaction mixture containing guanidine and formaldehyde, in proportions of between 1.5 and 3.5 moles of formaldehyde for each mole of guanidine, at a temperature between 20 and 80 C. for a period of time ranging from up to fifteen minutes at 80 C. to at least six hours at 20 C., the reaction time varying inversely with the reaction temperature and having a an aqueous reaction mixture of guanidine and formaldehyde at a temperature between about 20 and 80 C. for a period of time ranging from up to fifteen minutes at 80 C.
- reaction time varying inversely with the reaction temperature and having a maximum of about 24 hours at 20 C.
- said reaction mixture containing from 1.5 to 3.5 moles of formaldehyde per mole of guanidine and terminating said reaction of guanidine and formaldehyde upon the expiramaximum of about 24 hours at 20 C., and separating the resulting solid condensation product from said reaction mixture.
- a process for the production of guanidine-formaldehyde condensation products which comprises heating at 50 C. for about an hour an aqueous reaction mixture containing guanidine and formaldehyde in proportions of between 1.8 and 2.5 moles of formaldehyde for each mole of guanidine, there being present in said mixture at least one gram of guanidine per 10 grams of reaction mixture, whereupon a solid guanidine-formaldehyde condensation product is obtained, thereafter neutralizing said reaction mixture by the addition of acid thereto to a pH of between 5 and 9 and heating said reaction mixture while maintaining the pH thereof within the range of 5 and 9 until the condensation product is dissolved and a clear solution obtained.
- a 7. The process of claim 6, wherein said acid is hydroxyacetic acid and the reaction mixture is heated for a period of about 10 minutes.
Description
, 2,736,749 Patented Feb. 28, 1956 United States Patent Oflice Hoffman & Co., Inc., Providence, R. 1., a corporationv of Rhode Island No Drawing. Application June 10, 1952, Serlal No. 292,141
8 Claims. (Cl- 260-564) The present invention relates to. the preparation of I guanidine-formaldehyde condensation products suitable for use in improving the washfastness of substantive dyestufis on cellulosic materials.
It is a well known fact that direct or substantive dyestufis exhibit relatively poor fastness to washing when applied to cellulosic materials. To remedy this difficulty, numerous dye-fixing agents, including guanidine-formaldehyde condensation products, have been proposed, but, while these agents have been partially satisfactory, none has been adequate to give outstanding results under the generally accepted AATCC Wash Test No. 3.
It has now been found that by using certain specific reaction conditions, a guanidine-formaldehyde condensation product of markedly superior dye-fixing properties can be obtained. The principal object of the present invention, therefore, is the provision of a guanidine-formaldehyde condensation product which is uniquely superior to the guanidine-formaldehyde condensation products and other dye-fixatives hitherto available. 4
A further object of the invention is the preparation of guanidine-formaldehyde dye-fixing agents which are highly substantive and will enhance the fastness of dyeings sufficiently to withstand themost strenuous of washing conditions.
Another important object of the present invention is to provide novel procedures for producing such guanidine-formaldehyde condensation products of superior dyefixing characteristics.
Still another object of the invention is the provision of a guanidine-formaldehyde condensation product which, in addition to providing maximum dye-fixation, otfers the further advantages over prior dye-fixing agents of being readily soluble, neutral in pH, stable to storage and nonsensitive to sulfate ions.
Still further objects and the entire scope of applicability of the present invention will become apparent from the detailed description given hereinafter; it should be understood, however, that the detailed description and specific examples, while indicating preferred embodiments of the invention, are given by way of illustration only, since various changes and modifications within 'the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.
Briefly stated, the foregoing objects are accomplished, in accordance with the present invention, by reacting an aqueous solution of guanidine and formaldehyde under mild conditions of temperature and time. The resulting reaction mixture, after neutralization with acid and solubilization by heating, may be used in the aftertreatment of previously dyed cellulosic materials-in conventional manner to render substantive dyeings highly washfast.
The success of the invention resides, at least to a substantial extent, 'in the discovery that mild reaction conditions are essential for producing a condensation product showing maximum washfastness. More partiwlarly, it has been found that if the reaction between guanidine and formaldehyde is etfected at a temperature not greater than 2 about 80' C., rather than at the refluxing temperatures conventionally employed, for a relatively moderate time, dependent upon the temperature employed, condensation products possessing unusually superior dye-fixing properties can be obtained. The duration of the condensation reaction varies inversely over a fairly wide range, according to the particular temperature employed. At the upper limit of about 80' C., it has been found that the reaction time should not exceed fifteen minutes in order to obtain a condensation product of optimum dye-fixingcharacteristics. Somewhat inferior products are obtained when the reaction is carried out at this temperature for more than fifteen minutes, e. g., one-half hour, and a poor dye-fixative is obtained if the reaction is carried out at 80' C. for an hour or more. When using temperatures below the upper limit, e. g., 20 to 35' C., the reaction must, of course, be longer than that at 80 C. to give the best products. Generally speaking, the reaction times at these lower temperatures should not be less than six hours, and excellent results have been obtained using reaction times of 20 to 24 hours at these temperatures. Such reaction times, at the relatively low temperature employed, can be viewed as being mild reaction conditions, while reaction time of an hour or so at 80 C. should be considered vigorous conditions. In short, therefore, the present invention contemplates reacting guanidine and formaldehyde at a temperature up to about 80 C. for periods of time ranging from up to fifteen minutes at 80 C. to a period of at least six hours, and preferably about twenty to twenty-four hours, at temperatures of about 20 to 35 C. v
t A more complete understanding of the present invention may be had by reference to the following examples of actual operations in accordance with the invention. It will be understood, however, that these examples are given only for purposes of illustration and are not to be considered as in any way limiting the scope of the invention.
Example I This example is illustrative of a preferred procedure of carrying out the present invention.
To a solution of 38 grams (0.95 mole) of sodium hydroxide in 300 grams ofwater in a one liter 3-neck flask fitted with stirrer, condenser, and thermometer, there was added 95.5 grams (1.0 mole) of guanidine hydrochloride followed by 170 gramsv(2.l moles) of formaldehyde solution (37% by weight). The reaction mixture was then heated at 50 C. for one hour with stirring; After adding glacial acetic acid to pH 6.5 and then as required to maintain the pH 6.5 to 7.5 while heating,
the reaction mixture was refluxed for ten minutes and cooled. A total of 31 grams (0.52 mole) of glacial acetic acid was used. The clear, colorless solution weighed 637 grams.
For aftertreatment, cotton cloth, dyed with a substantive dyestuff, was treated at 170 F. for'one-half hour in a bath containing about 795% of this product (based on the weight of fabric) together with a copper compound. The thus aftertreated, dyed fabric demonstrated excellent washfastness upon exposure to the No. 3 AATCC Wash Test conditions.
Example II In a manner similar to that described in Example I, grams (0.50 mole) of guanidine carbonate was added to a solution of 44 grams l.l moles) of sodium hydroxide in 300 grams of water. Reaction with 162 grams (2.0 moles) of formaldehyde solution at'50". C. for one hour was followed by neutralization and solubilization as in Example I; grams (1.75 moles) of glacial acetic acid was used. Aftertreatment of dyed cotton fabric with the resulting product afiorded outstanding fastness to washing.
Example Ill Following a procedure similar to that described in Example I, 122 grams (1.0 mole) of guanidine nitrate was added to a solution of 40 grams (l.0 mole) of sodium hydroxide in Til-grams of water. After reaction with 162 grams (2 moles) of formaldehyde solution at 50 C. for one hour, neutralization and solubilization were carried out as in Example I; 36 grams of glacial acetic acid was required. I
Use of the product obtained above in the after-treatment of a dyed cotton fabric as outlined in Example I rendered the dyeing substantially washfast.
Example I V Free guanidine was obtained by stirring 360 grams (2 moles) of guanidine carbonate in 1300 ml. of water with 800 grams (2.5 moles) of finely ground barium hydroxide hydrate until complete reaction. The mixture was filtered and the solution balanced by adding sulfuric acid until a filtered sample gave no precipitate with sulfuric acid or barium chloride.
One-eighth of this solution (219 grams containing 0.50 mole of guanidine) was allowed to react with 81 grams (1.0 mole) of formaldehyde solution at 50 C. for one hour. Neutralization and solubilization, as in Example I, took grams of glacial acetic acid. The resulting product was found to markedly improve the washfastness of substantive dyeings on cellulosic fabrics, when used as an after-treatment in the manner of Example I.
Example V Forty-eight grams (0.50 mole) of guanidine hydrochloride was added to a solution of 18 grams (0.45 mole) of sodium hydroxide in 448 grams of water in a manner similar to that described in Example I. Reaction with 81 grams (1.0 mole) of formaldehyde solution at 50 C. for three hours was followed by neutralization and solubilization as before. dyed with a substantive dyestuff in the manner described in Example I, except that, in this case, twice the quantity of the solubilized product was employed, resulted in a dyeing which was substantially unaffected by exposure to No. 3 AATCC Wash Test conditions.
Example VI An identical procedure to that described in Example IV was followed, except that the condensation reaction was carried out at 65 C. for one hour. The resulting product gave results substantially identical with those of the product of Example I.
Example VII .the pH 6 to 6.5 while heating (47 grams was used). A
ten minute reflux period afforded a. clear, colorless solution which, when used in the manner of Example I, rendered a substantive dyeing on cotton essentially fast to washing.
Example VIII An identical procedure to that described in Example VII was followed, except that neutralization to pH 7 to 7.5 was accomplished with 32 grams of dilute sulfuric acid solution containing 21 grams of concentrated sulfuric acid with substantially equivalent results.
Example X The procedure of'Example I was followed, except that in place of sodium hydroxide, 62.5 grams of potassium hydroxide (U. S. P. pellets) was used and the amount of water was 267 grams. Results substantially identical to those shown in Example I were obtained.
Example XI Following a procedure similar to that described in Example I, 95.5 grams (1.0 mole) of guanidine hydrochloride was added to a solution of 40 grams (1.0 mole) of sodium hydroxide in 298 grams of water. After reaction with 162 grams (2.0 moles) of formaldehyde solution at 50 C. for one hour, the reaction mixture was cooled and allowed to stand at to C. for eighteen 'hours. The granular-like insoluble was removed by filtration and dried at room temperature to give a product weighing 87 grams. For use, 1.0 gram of this product was dissolved in 3000 ml. of water heated to 65 C. and,
p when this solution was used for aftertreatment of dyed Aftertreatment of a cotton fabric I cellulosic fabrics, the fastness properties of the dyeings were improved to a remarkable degree.
Example XII An identical procedure to that described in Example IV was followed, except that the condensation reaction was allowed to take place at 30 to 35 C. for sixteen hours. The resulting product gave results substantially identical with those of the product of Example IV.
Example XIII Following a procedure similar to that described in Example I, 95.5 grams (1 mole) of guanidine hydrochloride was added to a solution of 38 grams (0.95 mole) of sodium hydroxide in 302 grams of Water. After reaction with 170 grams (2.1 moles) of formaldehyde solution at 50 C. for one hour, 70% hydroxyacetic acid was added to a pH of 6 and then as required to maintain the pH between 6 and 6.5 while heating (56 grams of acid was used). A ten minute reflux period afforded a clear colorless solution which, when used in the manner of Example I, gave a substantially washfast substantive dyeing on cotton fabric.
Example XIV This example is illustrative of the results obtained using a procedure wherein, in contrast to the present invention, vigorous reaction conditions are employed.
A procedure identical with that described in Example IV was followed, except that a reaction temperature of C. was maintained for one hour. Substantive aftertreatme'nt with the product thus obtained resulted in poor washfastness, compared to that obtained using the product of Example IV.
The aqueous solution of guanidine and formaldehyde used in the process of the invention can be prepared in any convenient manner. For instance, free guanidine may be dissolved in water and the desired proportion of formaldehyde, in aqueous solution, added thereto. Alternatively, the reaction mixture is obtained in the preferred manner illustrated in the preceding examples, i. e., by adding aqueous formaldehyde to an aqueous solution of guanidine prepared by reacting a guanidine salt, such as the hydrochloride, nitrate or carbonate, with an approximately equivalent amount of a base stronger than guanidine, e. g., sodium or potassium hydroxide or with a compound, such as barium or calcium hydroxide, which reacts to form an insoluble salt capable of being separated from the guanidine solution.
Formaldehyde as such or in the form of its polymers, such as paraformaldehyde, may be used for reaction with the guanidine, in accordance with the present invention. Generally speaking, the amount of formaldehyde utilized is between 1.5 and 3.5 moles per mole of guanidine, although, preferably, there is employed from 1.8 to 2.5 moles of formaldehyde for each mole of guanidine.
After' eliecting reaction between the guanidine and formaldehyde, the resulting condensation product may be solubilized and, thereafter, applied to dyed cellulosic materials in any conventional fashion. Normally, solubilization is accomplished by adding to the reaction mixture an appropriate acid, such as formic, acetic, lactic, hydrochloric, sulfuric, or hydroxyacetic, the last being preferred, to a pH of about to 9, and preferably to a pH on the acid side of the stated range. After addition of the acid, the reaction mixture is refluxed until the condensation product is dissolved and a clear, colorless solution is obtained. This solution may then be used as an aftertreatment for dyed cellulosic fabric at a concentration of about 1% (calculated as organic solids on the weight of cloth) preferably in conjunction with known copper compounds. Alternatively, rather than neutralizing the reaction mixture and dissolving the condensation product, the latter may be recovered in solid form from the reaction mixture by filtration, thereafter dried and then dissolved in hot water for use in aftertreating dyed cellulosic materials in the manner above described. In either case, the washfastness of dyeings treated with the condensation products of the invention is remarkably superior to the washfastness of dyeings treated with the previously available dye-fixatives.
It will be appreciated that the foregoing description has been given only for purposes of explanation and that variations may be made in the procedures described without in any way deviating from the scope of the invention as outlined in the appended claims.
I claim:
1. A process for the production of guanidine-formaldehyde condensation products which comprises heating time ranging from up to fifteen minutes at 80 C. to
at least six hours at C., the reaction time varying inversely with the reaction temperature and having a maximum of about 24 hours at 20 C., thereafter neutralizing said reaction mixture by addition of acid thereto to a pH of between 5 and 9 and heating said reaction mixture until a clear solution is obtained.
4. The process of claim 3, wherein the acid added is hydroxyacetic acid.
' 5. A process for the production of guanidine-formaldehyde condensation products which comprises heating an aqueous reaction mixture containing guanidine and formaldehyde, in proportions of between 1.5 and 3.5 moles of formaldehyde for each mole of guanidine, at a temperature between 20 and 80 C. for a period of time ranging from up to fifteen minutes at 80 C. to at least six hours at 20 C., the reaction time varying inversely with the reaction temperature and having a an aqueous reaction mixture of guanidine and formaldehyde at a temperature between about 20 and 80 C. for a period of time ranging from up to fifteen minutes at 80 C. to at least six hours at 20' C., the reaction time varying inversely with the reaction temperature and having a maximum of about 24 hours at 20 C., said reaction mixture containing from 1.5 to 3.5 moles of formaldehyde per mole of guanidine and terminating said reaction of guanidine and formaldehyde upon the expiramaximum of about 24 hours at 20 C., and separating the resulting solid condensation product from said reaction mixture.
6. A process for the production of guanidine-formaldehyde condensation products which comprises heating at 50 C. for about an hour an aqueous reaction mixture containing guanidine and formaldehyde in proportions of between 1.8 and 2.5 moles of formaldehyde for each mole of guanidine, there being present in said mixture at least one gram of guanidine per 10 grams of reaction mixture, whereupon a solid guanidine-formaldehyde condensation product is obtained, thereafter neutralizing said reaction mixture by the addition of acid thereto to a pH of between 5 and 9 and heating said reaction mixture while maintaining the pH thereof within the range of 5 and 9 until the condensation product is dissolved and a clear solution obtained. A 7. The process of claim 6, wherein said acid is hydroxyacetic acid and the reaction mixture is heated for a period of about 10 minutes.
8. The guanidine-formaldehyde condensation products obtained by the process of claim 1, said products being characterized by improved dye-fixing characteristics.
References Cited in the file of this patent UNITED STATES PATENTS 1,780,636 Stine Nov. 4, 1930 2,093,651 Widmer et al. Sept. 21, 1937 2,123,152 Rivat July 5, 1938 2,123,153 Rivat July 5, 1938 2,145,011 Landolt- Jan. 24, 1939 2,234,905 Tallis Mar. 11, l94l 2,281,559 De'Alelio May 5, 1942 2,281,879 Joyne May 5, 1942 2,288,695 Fuller July 7, 1942 2,322,333 Widmer et al. June 22, 1943 2,362,915 MacGregor Nov. 14, 1944 2,458,397 MacGregor Jan. 4, 1949 2,462,428 Roesti Feb. 22, 1949 FOREIGN PATENTS 429,209 Great Britain May 27, 1935 435,871 Great Britain Oct. 1, 1935
Claims (1)
1. A PROCESS FOR THE PRODUCTION OF GUANIDINE-FORMALDEHYDE CONDENSATION PRODUCTS WHICH COMPRISES HEATING AN AQUEOUS REACTION MIXTURE OF GUANIDINE AND FORMALDEHYDE AT A TEMPERATURE BETWEEN ABOUT 20 AND 80* C. FOR A PERIOD OF TIME RANGING FROM UP TO FIFTEEN MINUTES AT 80* C. TO AT LEAST SIX HOURS AT 20* C. THE REACTON TIME VARYING INVERSELY WITH THE REACTION TEMPERATURE AND HAVING A MAXIMUM OF ABOUT 24 HOURS AT 20* C., SAID REACTION MIXTURE CONTAINING FROM 1.5 TO 3.5 MOLES OF FORMALDHYDE PER MOLE OF GUANIDINE AND TERMINATING SAID REACTION OF GUANIDINE AND FORMALDEHDE UPON THE EXPIRATION OF THE SAID REACTION TIME.
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2908543A (en) * | 1956-06-29 | 1959-10-13 | Gen Aniline & Film Corp | Aftertreatment of leather dyeings |
US2990425A (en) * | 1956-06-06 | 1961-06-27 | Ici Ltd | New biguanide salts |
US3002881A (en) * | 1956-11-09 | 1961-10-03 | Cons Mining & Smelting Co | Method of increasing the wet strength of cellulosic material and article formed thereby |
US3230213A (en) * | 1962-07-19 | 1966-01-18 | Charles L Mehltretter | Preparation of aminoguanidine derivatives |
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US1780636A (en) * | 1925-10-08 | 1930-11-04 | Du Pont | Substituted guanidine-aldehyde condensation product |
GB429209A (en) * | 1934-02-09 | 1935-05-27 | Chem Ind Basel | Improvements relating to processes of dyeing with direct dyestuffs |
GB435871A (en) * | 1933-04-05 | 1935-10-01 | Chem Ind Basel | Manufacture of preparations for improving textiles |
US2093651A (en) * | 1933-02-09 | 1937-09-21 | Gustave A Widmer | Dyeing fibrous materials |
US2123152A (en) * | 1934-11-13 | 1938-07-05 | Henry Dreyfus | Treatment of cellulosic materials |
US2123153A (en) * | 1935-04-04 | 1938-07-05 | Celanese Corp | Printing and other textile treatments |
US2145011A (en) * | 1935-02-23 | 1939-01-24 | Soc Of Chemical Ind | Process for matting textiles |
US2234905A (en) * | 1941-03-11 | Dyeing of cellulosic textile | ||
US2281879A (en) * | 1941-06-21 | 1942-05-05 | American Cyanamid Co | Preparation of organic base compounds |
US2281559A (en) * | 1939-08-09 | 1942-05-05 | Gen Electric | Urea-haloacylated urea-aldehyde condensation products |
US2288695A (en) * | 1939-07-26 | 1942-07-07 | Bell Telephone Labor Inc | Electrical insulated conductor |
US2322333A (en) * | 1938-07-04 | 1943-06-22 | Ciba Products Corp | Improving fastness of dyeings |
US2362915A (en) * | 1940-12-24 | 1944-11-14 | Courtaulds Ltd | Process for improving the fastness to washing of dyed cellulosic textile materials |
US2458397A (en) * | 1943-11-18 | 1949-01-04 | Courtaulds Ltd | Dyeing of nylon fibers by treating with nitrogenous condensation products |
US2462428A (en) * | 1943-10-29 | 1949-02-22 | Ciba Ltd | Process of dyeing glass fibers |
-
1952
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US2234905A (en) * | 1941-03-11 | Dyeing of cellulosic textile | ||
US1780636A (en) * | 1925-10-08 | 1930-11-04 | Du Pont | Substituted guanidine-aldehyde condensation product |
US2093651A (en) * | 1933-02-09 | 1937-09-21 | Gustave A Widmer | Dyeing fibrous materials |
GB435871A (en) * | 1933-04-05 | 1935-10-01 | Chem Ind Basel | Manufacture of preparations for improving textiles |
GB429209A (en) * | 1934-02-09 | 1935-05-27 | Chem Ind Basel | Improvements relating to processes of dyeing with direct dyestuffs |
US2123152A (en) * | 1934-11-13 | 1938-07-05 | Henry Dreyfus | Treatment of cellulosic materials |
US2145011A (en) * | 1935-02-23 | 1939-01-24 | Soc Of Chemical Ind | Process for matting textiles |
US2123153A (en) * | 1935-04-04 | 1938-07-05 | Celanese Corp | Printing and other textile treatments |
US2322333A (en) * | 1938-07-04 | 1943-06-22 | Ciba Products Corp | Improving fastness of dyeings |
US2288695A (en) * | 1939-07-26 | 1942-07-07 | Bell Telephone Labor Inc | Electrical insulated conductor |
US2281559A (en) * | 1939-08-09 | 1942-05-05 | Gen Electric | Urea-haloacylated urea-aldehyde condensation products |
US2362915A (en) * | 1940-12-24 | 1944-11-14 | Courtaulds Ltd | Process for improving the fastness to washing of dyed cellulosic textile materials |
US2281879A (en) * | 1941-06-21 | 1942-05-05 | American Cyanamid Co | Preparation of organic base compounds |
US2462428A (en) * | 1943-10-29 | 1949-02-22 | Ciba Ltd | Process of dyeing glass fibers |
US2458397A (en) * | 1943-11-18 | 1949-01-04 | Courtaulds Ltd | Dyeing of nylon fibers by treating with nitrogenous condensation products |
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Publication number | Priority date | Publication date | Assignee | Title |
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US2990425A (en) * | 1956-06-06 | 1961-06-27 | Ici Ltd | New biguanide salts |
US2908543A (en) * | 1956-06-29 | 1959-10-13 | Gen Aniline & Film Corp | Aftertreatment of leather dyeings |
US3002881A (en) * | 1956-11-09 | 1961-10-03 | Cons Mining & Smelting Co | Method of increasing the wet strength of cellulosic material and article formed thereby |
US3230213A (en) * | 1962-07-19 | 1966-01-18 | Charles L Mehltretter | Preparation of aminoguanidine derivatives |
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